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United States Patent | 6,232,353 |
Alexandratos ,   et al. | May 15, 2001 |
A cross-linked water-insoluble ion exchange resin comprised of polymerized monomers having a phenyl ring is disclosed. A contemplated resin contains (i) polymerized phenyl ring-containing monomers having a phosphonic acid ligand linked to the phenyl ring, (ii) about 2 to about 5 millimoles per gram (mmol/g) of phosphorus as phosphonic acid ligands, and (iii) a sufficient amount of a sulfonic acid ligand such that the ratio of mmol/g of phosphonic acid to mmol/g sulfonic acid is up to 3:1. A process for removing polyvalent metal cations from aqueous solution, and a process for removing iron(III) cations from acidic copper(II) cation-containing solutions that utilize the contemplated resin or other resins are disclosed.
Inventors: | Alexandratos; Spiro (Knoxville, TN); Shelley; Christopher A. (Knoxville, TN); Horwitz; E. Philip (Naperville, IL); Chiarizia; Renato (Elmhurst, IL) |
Assignee: | Arch Development Corporation (Chicago, IL) |
Appl. No.: | 221446 |
Filed: | December 28, 1998 |
Current U.S. Class: | 521/26; 210/673; 210/681; 423/139; 521/38; 526/222; 526/225 |
Intern'l Class: | C08J 005/20; C02F 001/42 |
Field of Search: | 521/26,38 210/673,681 423/139 526/225,222 |
2764563 | Sep., 1956 | McMaster | 260/2. |
3298969 | Jan., 1967 | D'Alelio | 260/2. |
4664700 | May., 1987 | Alexandratos. | |
5116882 | May., 1992 | Grey et al. | 521/147. |
5281631 | Jan., 1994 | Horwitz | 521/38. |
5449462 | Sep., 1995 | Horwitz et al. | 210/682. |
5582737 | Dec., 1996 | Gula et al. | 210/673. |
5948264 | Sep., 1999 | Dreisinger et al. | 210/673. |
Marcel Dekker Catalog: Solvent Extraction Ion Exchange, Publication date information, published at http://www.dekker.com/e/p.pl/0736-0299 (information downloaded Mar. 13, 2000).* Chiarizia, et al., "Uptake of Metal Ions by a New Chelating Ion-Exchange Resin, Part 4: Kinetics," Sov. Extr. Ion Exch., 12(1):211-237 (1994). Bogoczek. et al., "Synthesis of Phosphorus-Containing Wofatit Cation Exchangers and Their Affinity Toward Selected Cations," J. Appl. Polym. Sci., 26:4161-4173 (1981). Cassidy, "Electron-Transfer Polymers (Oxidation-Reduction Polymers)," J. Polym. Sci.--Part D, 1-58 (1972). Alexandratos, et al., "Dual Mechanism Bifunctional Polymers: Polystyrene-Based Ion-Exchange/Redox Resins," Macromolecules, 19:280-287 (1986). Alexandratos, et al., "Bifunctionality as a Means of Enhancing Complexation Kinetics in Selective Ion Exchange Resins," Ind. Eng. Chem. Res., 34:251-254 (1995). "Brine Purification" Duolite product pamphlet. Levin, et al., "Radical Copolymerization of Monovinyl Derivatives of Phosphorus," Vysokomol. Soedin., Ser., 17:845-854 (1975) and Chem. Abstr. database entry regarding the same. Su, et al., "Application of a macroporous resin containing imidazoline groups to preconcentration and separation of gold, platinum and palladium prior to ICP-AES determination," Talanta 42: 1127-1133 (1995). Lan, et al., "Synthesis, properties and applications of silica-immobilized 8-quinolinol," Analyt, Chim, Acta, 287: 101-109 (1994). Lezzi, et al. Chelating Resins Supporting Dithiocarbamate and Methylthiourea Groups in Adsorption of Heavy Metal Ions, J. App., Polym. Sci., 54: 889-897 (1994). Kamble, et al. "Synthesis and Characterization of Oxime Resin of Poly (4-vinyl, 2'-carboxybenophenone) and Its Metal Polychelates," J. App., Polym. Sci., 56: 1519-1521 (1995). Tomita, et al. Synthesis and Radical Polymerization of Styrene Derivative Bearing Kojic Acid Moieties, J. Polym. Sci . . , Part A: Polym. Chem., 34: 271-276 (1996). Tomoi, et al. "Mechanisms of Polymer-Supported Catalysts. 1. Reaction of 1-Bromooctane with Aqueous Sodium Cyanide Catalyzed by Polystyrene-Bound Benzyltri-n-butylphosphonium Ion" J. Am. Chem. Soc., 103: 3821-3828 (1981). Van Berkel, et al. "Metal Uptake by Didentate and Tridentate Pyrazole-Containing Ligands Immobilized onto Poly (Glycidyl Methacrylate-Co-Ethylene Glycol Dimethacrylate," Eur. Polym. J., 28, (7): 747-754 (1992). Kawamura, et al. "Adsorption of Metal Ions on Polyaminated Highly Porous Chitosan Chelating Resin," Ind. Eng. Chem. Res., 32: 386-391, (1993). Buchanan, et al. "Poly (vinylbenzo macrocyclic polyethers). Synthesis and cation binding properties of 12-crown-4 derivatives," Can. J. Chem., 69: 702-705 (1991). Alexandratos, et al., "Enhanced Ionic Recognition by Polymer-Supported Reagents: Synthesis and Charaterization of Ion-Exchange/Precipitation Resins," Macromolecules, 21: 2905-2910 (1988). Treochimczuk et al., "Synthesis of Bifunctional Ion-Exchange Resins through the Abrusov Reaction: Effect on Selectivity and Kinetics," J. Appl. Polym. Sci., 52: 1273-1277 (1994). Alexandratos, et al., "Synthesis and Ion-Complexing Properties of a Novel Polymer-Supported Reagent with Diphosphonate Ligands," Macromolecules, vol. 29: 1021-1026 (1996). Horwitz et al., "Uptake of Metal Ions by a New Chelating Ion-Exchange Resin. Part 1: Acid Dependencies of Actinide Ions," Solv. Extr. Ion Exch., vol. 11 (5): 943 (1993). Chiarizia, et al., "Uptake of Metal Ions by a New Chelating Ion-Exchange Resin. Part 2: Acid Dependencies of Transition and Post-Transition Metal Ions," Solv. Ext. Ion Exch., vol. 11(5) : 967 (1993). Bindert K. Vriesema, et al. "Synthesis of Aza Macrocycles by Nucleophilic Ring Closure with Cesium " J. Org. Chem. 49: 110-113 (1984). |
TABLE 1 Characterization of Bifunctional Phosphonic/Sulfonic Acid Ion Exchange Resins Acid Percent Solids Capacity P Capacity Percent DVB (g.sub.dry /g.sub.wet) .times. 100 (mmol/g) (mmol/g) 2 33.7 10.89 3.52 12 63.4 9.03 3.10 25 71.2 6.88 1.95
TABLE 2 Characterization of Monofunctional Phosphonic Acid Ion Exchange Resins Acid Percent Solids Capacity P Capacity Percent DVB (g.sub.dry /g.sub.wet) .times. 100 (mmol/g) (mmol/g) 2 51.2 9.88 4.94 12 76.0 7.69 4.10 25 83.0 4.84 2.55
TABLE 3 Complexation of Eu (III) from 10.sup.-4 N Eu(NO.sub.3).sub.3 /HNO.sub.3 Solutions Using Phosphonic/Sulfonic Acid Resins Percent 0.01N 0.10 0.50N 1.00 DVB HNO.sub.3 HNO.sub.3 HNO.sub.3 HNO.sub.3 2 >99% >99% 98.5% 95.3 (2350) (734) 12 >99% >99% >99% >99% 25 >99% >99% >99% >99%
TABLE 4 Complexation of Eu (III) from 10.sup.-4 N Eu(NO.sub.3).sub.3 /HNO.sub.3 Solutions Using Phosphonic Acid Resins Percent 0.01N 0.10N 0.50N 1.00N DVB HNO.sub.3 HNO.sub.3 HNO.sub.3 HNO.sub.3 2 >99% >99% 56.7% 17.2 (64.8) (10.3) 12 >99% >99% 28.3% 7% (13.1) (3.3) 25 91.6% 25.8% 4% 6% (277) (8.80) (1.1) (1.7)
TABLE 5 Complexation of Eu (III) from 10.sup.-4 N Eu(NO.sub.3).sub.3 /0.40N NaNO.sub.3 /HNO.sub.3 Solutions Using Phosphonic/Sulfonic Acid Resins Percent 0.01N 0.10N 0.50N 1.00N DVB HNO.sub.3 HNO.sub.3 HNO.sub.3 HNO.sub.3 2 >99% >99% >99% 92.7 (451) 12 >99% >99% >99% >99% 25 >99% >99% >99% 98.6% (1400)
TABLE 6 Complexation of Eu (III) from 10.sup.-4 N Eu(NO.sub.3).sub.3 /0.40N NaNO.sub.3 /HNO.sub.3 Solutions Using Phosphonic Acid Resins Percent 0.01N 0.10 N 0.50N 1.00N DVB HNO.sub.3 HNO.sub.3 HNO.sub.3 HNO.sub.3 2 >99% 97.6% 50.4% 15.7% (2010) (50.2) (9.2) 12 >99% 94.2% 26.0% 6% (670) (14.4) (2.6) 25 81.1% 9% 8% 9% (107) (2.5) (2.3) (2.6)
TABLE 7 Column Loading. DIPHONIX .RTM. DUOLITE .RTM.C-467 CS3-104 [Fe.sup.+3 ] Load 1.951 g/L 1.886 g/L 1.957 g/L Solution Fe.sup.3+ Fe.sup.3+ Fe.sup.3+ [Cu.sup.2+] Load 39.94 g/L 39.60 g/L 39.77 g/L Solution Cu.sup.2+ Cu.sup.2+ Cu.sup.2+
TABLE 8 Iron Concentrations During Loading (g/L Fe) DUOLITE .RTM. Bed Volumes DIPHONIX .RTM. C-467 CS3-104 2 0.0000 0.0550 0.0040 4 0.0042 1.3361 0.0076 6 0.0786 1.7566 0.1234 8 0.7157 1.8167 0.4754 10 1.3710 1.8285 0.7729 15 1.7550 1.8449 1.1006 20 1.9620 1.8520 1.3400 25 1.9140 1.8750 1.5113 30 1.9300 1.8682 1.5965 35 1.9380 1.8367 1.6619 40 1.9350 1.8182 1.6994 50 1.7457 60 1.8334 70 1.8422
TABLE 8 Iron Concentrations During Loading (g/L Fe) DUOLITE .RTM. Bed Volumes DIPHONIX .RTM. C-467 CS3-104 2 0.0000 0.0550 0.0040 4 0.0042 1.3361 0.0076 6 0.0786 1.7566 0.1234 8 0.7157 1.8167 0.4754 10 1.3710 1.8285 0.7729 15 1.7550 1.8449 1.1006 20 1.9620 1.8520 1.3400 25 1.9140 1.8750 1.5113 30 1.9300 1.8682 1.5965 35 1.9380 1.8367 1.6619 40 1.9350 1.8182 1.6994 50 1.7457 60 1.8334 70 1.8422
TABLE 10 Recirculating Eluant Iron Amounts (g Fe) DUOLITE .RTM. DIPHONIX .RTM. C-467 CS3-104 0.5 hours 0.0038 0.00202 0.00450 1 hour 0.00591 0.00423 0.00797 2 hours 0.01019 0.00448 0.00886 3 hours 0.00909 0.00451 0.00877 4 hours 0.01191 0.00476 5 hours 0.01212
TABLE 11 Column Regeneration DUOLITE .RTM. DIPHONIX .RTM. C-467 CS3-104 Steady State 3.741 g/L Fe 1.418 g/L Fe 2.712 g/L Fe [Fe] Final 118.6 mL 97.8 mL 59.9 mL circulating eluant volume Total iron 0.49646 g 0.15870 g 0.19254 g in final circulating eluant Iron 104.8% 96.1% 108.2% Recovery